Production of organo-boron compounds



, producing organo-b'oron; compounds and; :hass-particulan '.'reference to the PI'OdllCtlOIl OfiibOlflZClCS.

United States Patent 5 s --2;978-,s02 j. is PRODUCTION OF oncANo-nonoN'cor/iroufibs William David English, Garden Grove, and Allen L. aMcCloskeyflcfirangeg:Califgrnssignors to United States Borax Sr-Chemical; Gorpration,;,-LOS A QIESyICaIiL,

' a-corporation'of Nevada U 1 No Drawing. File'd Mart-6; 1959,Sei :"No; 197,565

4 Claims; (Cl. 260-5551 J'IThiS invention relateseas: indicated: to. for

The class of materials knowmasiibo'razoles'are;heterocyclichexatomic ringcompounds Eliavirigsth'e: general nformula (BH+NH) ,":ands:anyisubstituentsi of the' ringrzare named with N or B prefixes to designateatheirpos'i-i tions. The present inventionis' concerneditwith' a pari ticular: group of "borazoles wherein: the -N=ic is substituted :.-with= alkyl or aryl r'adicalsy and -the:B-" isns'ubstituted with alkylamino or arylamino radicals. This .group of barozoles I can be inferred to. generically :as" Btrialkylamino-N-trialkylborazoles and B-triarylamino-Natriarylbora zoles. I Additionally?"these: compoundst can be? mix- 1 mes: of the foregoingi'such as: Batriarylamino N-trialkyl- 5 b ora zoles or B-trialkylamino Ntriarylborazoles.

" It is; therefore, the 'principaliobject 'ofxthis invention to.

- iprovide "a method'for making borazoles wherein the "N is substituted :with alkyl andloriaryl" radicals; andtthe -"B is substituted with alkylaminoiiandfior arylamino:rad-

- icals.

if-Other objects will "appeal-as 'thelde'scription'.1proceeds.

i To the accomplishment of--the"foregoing:;and related -ends,- the invention 1 then comprisesithe' features 'her'einafter-"fully described and pointediout' in=the claims,'the

'- following description setting forth' in detail certainl illusof the inventionmay be "employed.

t trative embodiments'of theiinvention, these beingtindicative, however, of but a few ways in which the principle "Broadly stated; the: present invention -cornprisesthe method of producing borazoleswhich'c'omprisesthe reaction of a material selected from the group consisting of @(RNHMB and,(R N) B wherein R is a materialfsel'ected from the group consisting; of alkylradicals havingtfrom 1-6 carbon atoms; phenyl, thiophenyl,-2 andl'spyridylu'adicals with a material selected from the group of amine salts bf: strongflprotonic acids consistingfof RNHg-zHA,

" R NH :HAand 'RgNzHA whereinRi is" amaterial' selected from the group consisting' of alkyl radica'lsi:having-from 1-6 carbon atoms, phenyl, thiophenyl and pyridyl radicals, HA is a strong protonic acid, 'andWhrin at least one of said reaction ingredients is derived: from a primary am n in the reaction but acts as a catalyzer.

portant factors in the above broadly stated paragraph. It is immaterial to the present invention whether the R groups of both reaction ingredients are all the same or all different. Thus, for example, isopropylarnine hydrochloride can be reacted with tris(isopropylamino)borane to produce B-tris(isopropylamino)-N-tri-isopropylborazole, or triethylamine sulfate can be reacted with tris- (anilino)bor'ane to produce B-tris(anilino)-N triphenylb orazole Secondly, it will be seen that at least one of the reaction ingredients must be derived from a primary amine. Thirdly, and of the utmost importance, it will be noted that the strong protonic acid does not take part The amine salt of any strong protonic acid can be used to catalyze the Patented ;Apr. A, 1961 ;;--;touic=;acididoesinotienter into;themeactiomandldoes not become part of thev borazolei':mbleculep Whether there' is an interchange of alkylamino groups or no interchange, -'the 'pi-otonici'acid only acts to catalyze" the reacntennermm theborazole'inolecul' I a p The following listis aniample of the many aniinoboi'anes' which' caiie eon ertedf'to boraioles according to the present method: 7

A'YPfimary aminoboranes: v

v 1) Tris(methyl amino) borane 2) Tris'(ethylainino)borane ,7

.. ,(3); Tris(urpropylamifio) borane (4') 'Tris(isoprepylaminwborane, (-5')" Tris(n-butylaminol'borane (6) "Tris(sec butylaniino)borane (7) Tris (tert-butylarnino)borane' (8) Trisfisobutylamino)borane .(9) Tris(amylamino);borane 1 (10) Tris(sec-amylamin0)borane i(' 1 1)jTris(tert-amylamino) bo'rane (12) Tris(hexylamino)b orane 1 l3) 'Tris ('se;c-hexylamino)borane (1'4) Tris(tert-hexylamino).boran e ('15) Tr is(anilino)borane" (16) Tris(pyridylamino;)borane v v (17) Tris(thiophenylamino)boraner" i B..Secondary a-minoboraneszl (1)Tris(diinethylamino)bbliane i (2). Tris(diethylamino) borane (3 Tris di-n-butylamino) borane v (4) 'Tris(di-isopropylarnino)borane- 5) Tris(allylmethylamino)boraue (6 )-,Tris(vN=methylanilino)borane j, I 7 Tris(diphenylaiiiindworane i1; o (8 Tris(pyrrolo)borane 5o i 4 aThefbilow ng ti aniil u trati es rleqtthema y amine salts of strong protpnic acids to the present invention:

"A.,-, Priina'rjy.a rriine 's altspf strong protonic acids: 1;

, (,1)QMethylarninohydrocliloridelhydrobroniid;.$ul- -..zfatljtrifluoracetate' Ethylaril ine-lliydibchlo'ri fate,".tr.if lub racetate.

V 3 Tcrt-butylamine hydrochloride,

V hydrobromidtg sulfate, trifluoracetate which are applicable 3 (9) Amylamine-hydrochloride, hydrobromide, sulfate, trifluoracetate (10) Sec-amylamine-hydrochloride, hydrobromide,

sulfate, trifluoroacetate (11) Tert-amylamine-hydrochloride, hydrobromide, sulfate, trifluoracetate (12) Hexylamine-hydrochloride, hydrobromide, sulfate, trifluoracetate (13) Sec-hexylamine-hydrochloride, hydrobromide,

sulfate, trifluoracetate (14) Pyrrolo-hydrochloride, hydrobromide, sulfate,

trifluoracetate (l) Aniline-hydrochloride, hydrobromide, sulfate,

tn'fiuoracetate r (16) Pyridylamine-hydrochloride, hydrobromide, sulfate, trifluoracetate' a f a (17) Thiophenylamine hydrochloride, hydrobromide, sulfate,trifluoracetate r B. Secondary amine salts of strong protonic acids:

(1) Dimethylamine-hydrochloride, hydrobromide,

sulfate, trifluoracetate Y (2) Diethylamine-hydrochloride, hydrobromide, sulfate, trifluoracetate (3) Di-n-butylamine-hydrochloride, hydrobromide,

sulfate, trifluoracetate (4) Di-isopropylamine-hydrochloride, hydrobromide,

sulfate, trifluoracetate (S) Allylmethylamine-hydrochloride, hydrohromide,

sulfate, trifluoracetate (6) N-methylaniline-hydrochloride, hydrobromide,

sulfate, trifluoracetate (7) Diphenylamine-hydrochloride, hydrobromide,

sulfate, trifluoracetate C. Tertiary amine salts of strong protonicacids:

(l) Trimethylamine-hydrochloride, hydrobromide,

sulfate, trifluoracetate (2) Triethylamine-hydrochloride, hydrobromide, sulfate, trifluoracetate v (3) Tri-n-propylamine-hydrochloride,' hydrobromide,

sulfate, trifluoracetate (4) Tri-n-tributylamine-hydrochloride, hydrobromide, sulfate, trifluoracetate (5) Tri-isobutylaminehydrochloride, hydrobromide,

sulfate, trifluoracetate (6) Trihexylamine-hydrochloride, hydrobromide, sulfate, trifluoracetate (7) Triphenylamine-hydrochloride, hydrobromide,

sulfate, trifluoracetate (8) Pyridine-hydrochloride, hydrobromide, sulfate,

tn'fluoracetate o (9) Quinoline-hydrochloride, hydrobromide, sulfate,

trifluoracetate' So that the present invention can be more clearly understood, the following illustrative examples are given:

Nineteen parts of isopropylamine hydrochloride and 37 parts of tris(isopropylamino)borane were heated at reflux until evolution of isopropylamine ceased, about 40 hours. The mixturewas cooled, triturated with petrolcum etherand filtered. The filtrate was distilled and yielded B-tris(isopropylamino) N triisopropylborazole,

Thirty parts of tris(isopropylamino)horane and 12 parts of methylarnine hydrochloride were heated together for 60 hours and then treated as in Example I. Distillation of the filtrate yielded triisopropyltrimethyl-B-triaminohorazole, B.P. 134-142/1 mm., n 1.4761. Chemical analysis showed 10.9% B and 26.9% N.

Thirty parts of tris(anilino)borane and 15 parts of trimethylamine sulfate were heated at reflux for about 70 hours. The product was recrystallized from triethylamine and then from chloroform to yield B-tris(anilino)- N-triphenylborazole, a white powder which turned brown on standing.

It is well known to those skilled in the art that the presence of boron in gasoline advantageously affects the ignition and octane rating of thegasoline. The borazoles of the present invention when added to gasolinewill be found to provide an improvedfuel for internal combustion engines. Further the present borazoles when added to diesel oil will aid in preventing sludging of the oil, and when added to jet aircraft fuel will act as an antiicing agent.

Other modes of applying the principle of the invention may be employed provided the features'stated in any of group of amine salts of strong protonic acids consisting of RNH HA, R NH HA and R N HA wherein R is a material selected from the group consisting of alkyl radicals having from 1-6 carbon atoms, phenyl, thiophenyl and pyridyl, HA is a strong protonic acid selected from the group consisting of hydrochloric, hydrobrornic, sulfuric and trifluoroacetic acids and wherein at least one of said reaction ingredients is derived from aprimary am1ne.. t t

2. The method of producing B-tris(isopropylamino)- N-triisopropylborazole which comprises heating at reflux tris(isopropylamino)borane with isopropylamine hydrochloride.

3. The method of producing triisopropyltrimethyl-B- triaminohorazole which comprises heating at reflux,tris- (igopropylaminwborane with methylarnine, hydrochlor1 e. .1 i

4. The method -of. producing .B-tris(anilino)-N-triphenylborazole whichicomprises heating at reflux tris- (anilino)borane with trimethylamine sulfate.

References Cited-in the, file of this patent UNITED STATES PATENTS H 2,821,463 Scott et al. Jan. 28,1958 

1. THE METHOD OF PRODUCING BORAZOLES WHICH COMPRISES HEATING AT REFLUX A TRIS(AMINO)BORANE SELECTED FROM THE GROUP CONSISTING OF (RNH)3B AND (R2N)3B WHEREIN R IS A RADICAL SELECTED FROM THE GROUP CONSISTING OF ALKYL RADICALS HAVING FROM 1-6 CARBON ATOMS, PHENYL, THIOPHENYL AND PYRIDYL, WITH A MATERIAL SELECTED FROM THE GROUP OF AMINE SALTS OF STRONG PROTONIC ACIDS CONSISTING OF RNH2 : HA, R2NH : HA AND R3N : HA WHEREIN R IS A MATERIAL SELECTED FROM THE GROUP CONSISTING OF ALKYL RADICALS HAVING FROM 1-6 CARBON ATOMS, PHENYL, THIOPHENYL AND PYRIDYL, HA IS A STRONG PROTONIC ACID SELECTED FROM THE GROUP CONSISTING OF HYDROCHLORIC, HYDROBROMIC, SULFURIC AND TRIFLUOROACETIC ACIDS AND WHEREIN AT LEAST ONE OF SAID REACTION INGREDIENTS IS DERIVED FROM A PRIMARY AMINE. 